Apparatus for conversion of hydrocarbons



J. MCAFEE APPARATUS FOR CONVERSION OF' HYDROCARBONS Filed June 15, 1'946 esse( UNITEDv STATES OFFICE APPARATUS FOR CONVERSION 0F HYDROCARBON S Jerry McAfee, Port Arthur, Tex., assigner to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Original application March 12, 1943, Serial No. 478,935. Divided and this application .lune 15, 1946, Serial No. 676,982 v 2 Claims. (Cl. ,Z3-288) 2 This is a division oi my pending application and between a conned reaction zone and a Serial No. 473,935, filed March l2, i943, now Patseparate'V confined combustion Zone, whereby the ent No, 2,420,145. carbonaceous deposits are continuously burned This invention is directed to an improved procfrom the contact material and the latter is coness and apparatus of the type wherein reactants 5 tlnuously heated and supplied in. heated state to be treated or converted are contacted with a to the reaction zone to maintain a substantially mass of solid material in which the heat reuniform temperature in the latter. In this imquired for conducting the desired reaction has proved Operation there is no periodic Switching been stored. of the reactants from one vessel to another, the The features of the invention. are particularly l@ reaction zone being continuously -operated for directed to a process for the thermal decomposicon-version of the hydrocarbons and the comtion of' hydrocarbons at relatively high temperabustion zone being continuously operated for ture and low effective pressure to produce lighter heating the lContact material. and more valuable hydrocarbons, such as buta- In the preferred embodiment of the invention, diene, acetylene, etc. The subsequent description if) the bed of subdivided solid contact material in Will therefore be directed principally to this parthe reaction zone and the bed of the subdivided ticular reaction, but certain features of the insolid contact material in the combustion zone vention will be found advantageous in numerous are maintained in turbulent huid-like condition other contact reactions of the general type rst resembling that of a boiling liquid. In the reacmentioned above and are therefore not limited ru tion zone, this fluid-like cond1t1on of the bed of to use in conducting any specic reaction. contact material is obtained by passing the nui-d The reaction whereby hydrocarbons are therhydrocarbon reactants and resulting vaporous mally decomposed in an operation employing and gaseous conversion products through the relatively high cracking temperature, low presbed at a net upward velocity greater than that sure and short conversion time is well known. :ze ofv the subdivided solid material comprismg the To obtain the desired operating conditions it bed. As applied to the combustion zone, the has been common practice to employ recuperaluidizing. medium comprises air or other tive heaters containing a static bed or checkeroxygen-containing gas. employed to support comwork of re clay shapes or other refractory solid bustion of the fuel. The turbulent iiuid-like in which heat for conducting the reaction is pe- 3,

riodically stored by burning fuel in contact with uniform distribution of heat throughout the re the refractory material. For continuous operaaction Zone and throughout thev combustion Zone, tion, two or more such heaters are utilized and and, in combination with. the provision for conare eachalternately operated asV a reaction zone, tinuous circulation of the contact material bethrough which the hydrocarbon reactants and l tween the reaction and the regenerating zones, resulting conversion products are passed in contact with the heated reiractories, and as a comess lat a substantially constant and optimum bustion zone in which fuel is burned to store heat temperature level.

in the refractories. Heavy carbonaeeous or hy- The production of valuable light hydrocarbons, drocarbonaceous deposits accumulated in the reo such as butadiene and acetylene, by the high fractory mass during the conversion reaction temperature cracking of heavier hydrocarbons serve as fuel for heating the reiractoriesin the (either normally liquid or normally gaseous) is combustion step of the process. The operation best accomplished at low pressure (substantially is characterized by relatively short processing atmospheric or preferably sub-atmospheric) and steps with frequent periods of reheating. This with a relatively short time of exposure for the is necessitated by the rapidly decreasing' temhydrocarbons to the high temperature employed. perature of the refractory mass as the conver- A iluidized bed of contact material in the reacsion period progresses` and by the relatively large tion zone, as provided by the invention, is adamount of carbonaeeous deposits which tend to vantageous in that it reduces the pressure drop foul the refractory mass. 50 encountered by the hydrocarbons in passing In the improved operation provided by the in through the bed, as compared with the pressure vention, as applied to the type of reaction above drop encountered in, a static bed, and thus permentioned, I employ a moving mass of finely submits operation at a lower effective pressure. With divided solid contact material of a refractory nathe bed of contact material in iluidized conditure and circulate the same in series through 55 tion, the reaction zone may be operated at a gauge pressure only slightly without the use of a costly vacuum pump or exhauster for the outgoing products and, by introducing steam or other relatively inert gas to above atmospheric the reaction zone, a partial pressure for the hydrocarbon reactants well below atmospheric may be achieved.

Steam or other relatively inert gas to produce a partial pressure eifect and reduce the effective operating pressure has been previously used in reactions of the type above mentioned employing a stationary mass of solid refractory or contact material. The disadvantage of using steam in such operations is due to the additional equipment and expense involved in generating and superheating the large volumes of high temperature steam required. The use of other relatively inert gas involves the cost of compressing and heating the same for injection into the reaction zone. As a special feature of the invention, the same equipment which is utilized for conducting the conversion reaction and for reheating the subdivided solid contact material may be employed for the generating and/or superheating of the steam utilized in the reaction zone. This is accomplished by introducing water or low temperature steam into contact with the hot subdivided solid material passing from the combustion zone to the reaction zone. Heat thus imparted to the water or low temperature' steam results in the production of superheated steam which is supplied to the reaction zone with the contact material and, in one embodiment of the invention, the steam thus generated or superheated serves as a transporting fluid which, by its gas lift action, effects transfer of the subdivided solid contact material from thecombustion zone to the reaction zone.`

When liquid hydrocarbons of the nature of gas oil or heavier are employed as the charging stock, combustion of the heavy hydrocarbonaceous deposits accumulated on the contact material may store a sufficient quantity of heat in the latter to satisfy the requirements of the endothermic hydrocarbon conversion reaction. In other instances, and particularly when substantial quantities of steam are employed in the reaction zone, the additional heat necessary for conducting the conversion reaction and for bringing the steam to the required high reaction temperature may be stored in the contact material by burning additional fuel from an external source in the combustion Zone and by circulating the subdivided solid contact material through the system at a sufficiently rapid rate to transfer the required heat from the combustion zone to the reaction Zone.

In the preferred embodiment of the invention, I employ the lower portion of the reaction vessel as a steam superheating zone and establish a local cycle of contact material from this zone to the combustion zone and back to the steam superheating zone, in addition to circulating contact material from a higher point in the reaction vessel to and through the combustion zone and thence back through the steam superheating zone to the reaction zone. This, in conjunction with burning of the required additional fuel in the combustion zone makes possible the transfer of any desired quantity of heat from the combustion zone to the reaction Zone without excessively rapid circulation of the contact material through the reaction Zone. In other words, the desired residence time for the contact material in the zone wherein it contacts the hydrocarbons 4 z to be converted may be maintained independently of the rate of circulation required to eii'ect superheating of the steam employed.

The features and advantages of the invention are further explained in conjunction with the following description of the accompanying diagrammatic drawing.

The drawing is an elevational View, shown partially in section, one specific form of apparatus employing the features of the invention and in which the improved process provided by the invention may be conducted.

Referring to the drawing the reaction vessel is designated by the reference numeral 2 and comprises an elongated, vertically disposed, substantially cylindrical vessel within which is disposed la, fluidized bed of subdivided solid contact material indicated at 3. In the particular instance illustrated the reaction vessel is divided by a partition comprising an inverted truncated cone into an upper section, wherein the hydrocarbon reactants to be converted and resulting conversion products contact the uidized bed of subdivided solid material, and a lower section, designated in the drawing as a steam superheating zone, into which low temperature steam or liquid water is introduced and wherein the steam supplied to or generated therein is heated to approximately the temperature desired for conducting the hydrocarbon conversion reaction by its Contact with the fluidized bed of subdivided solid contact material maintained within this zone.

High temperature steam and subdivided solid contact material from the fluid bed in the lower section of the reaction vessel are directed through the central opening 5 in partition l into the upper section of the fluid bed, and the hydrocarbons to be converted are also introduced through line 5 and valve l into the lower portion of this upper section of the fluid bed. The hydrocarbons may be supplied to the reaction zone in preheated or in relatively cold state and in either liquid, vaporous or gaseous condition or in mixed phase.

The net upward velocity of the steam end of the hydrocarbon vapors and gases passing through the reaction vessel is greater than the net upward velocity of the particles of subdivided solid contact material` This results in the phenomenon known as hindered settling whereby the bed of solid particles is maintained in a turbulent fluid-like condition resembling that of a boiling liquid. This results in thorough and intimate mixing of the steam and solid particles in the lower section of the reaction vessel and thorough mixing of the steam and solid particles with the hydrocarbons in the upper section of the Vessel, so that a substantially uniform temperature prevails in each of these Zones and, due to the dispersed condition of the beds of solid particles, relatively low pressure drop is encountered by the steam, hydrocarbon reactants and resulting uid conversion products in passing through the bed.

The concentration of solid particles in the upper portion of the iiuid bed is materially less than their concentration in the lower portion of the bed. Thus the bed has a relatively light upper phase and a relatively heavy or more dense lower phase, the approximate line of demarcation between the light and dense phases in the reaction Zone being indicated by the broken line 8.

Vaporous and/or gaseous hydrocarbon conversion products, steam and entrained solid para major portion of the solid particles are centrifugally separated going stream it preferably passes through suitable heat recovery equipment such as a hot gas waste heat boiler' or other heat exchanger wherein readily available heat is recovtherefrom resulting heated contact material is continuously returned to the reaction vessel. To effect the transportation of contaminated solid particles from the dense phase of the fluid bed in the upper section of the reaction vessel a column wherein solid particles are stream of air or other oxygen-containing gas introduced to line IS through line i1 and valve I8. The oxidizing gas transports the solid particles into the lower portion of the regenerating vessel by its gas-lift action and keeps the bed of subdivided solid material maintained in this vessel in a turbulent huid-like congenerating vessel also supports combustion of the carbonaceous or the hydrooarbonaceous deposits on the Contact material With the result that the solid particles are heated to a high temperature in the regenerating zone. The turbulent fluidlike condition of the bed results in a substantially uniform temperature throughout the lat- -through'conduit 22 to the densephase 'of the Iiuid bed in the regenerating zone and combustion gases are directed from separator '2i through line 23, preferably to suitable heat recovery equipment of a desired type, not illustrated, wherein readily available heat is. recovered therefrom for use within the system or elsewhere as desired.

Hot subdivided solid material from the uid bed in the regenerating zone is returned via the before it comes into cont-act with the hydrocarbon reactants.

To eifect the transportation of subdivided solid contact material from the Iiuid bed in the regenerating zone to the fluid bed in the steam superheating zone a column thereof is directed downwardly from the dense phase of the fluid bed in thev regenerating zone through standpipe Z4 and throughV a suitable restriction, such 1as the adjustable orice indicated as a valve and designated. bythe reference numeral 25, disposed adjacent the lower end of standpipe 24, into transfer line 2K5. The hot Isolid particles are commingled in line 26 with water or low temperature steam supplied thereto through line 21 and valve 23'. The water and/or steam serves as a transporting fluid for the solid particles through the transfer line and the mixture is directed therefrom upwardly into the lower portion of the iiuid bed in the steam superheating zone.

When low temperature or saturated steam is supplied to the transfer line 26, the hot solid Contact material with which it is commingled in this line and in the lower portion of the fluid bed in the reaction vessel serves to heat it substantially to or above the desired reaction temperature to be employed for 'converting the hydrocarbons beforev the steam comes into contact with the latter in the reaction zone. When liquid water is supplied to the transfer line it is vaporized in the latter and/or the lower section of sired reactionv temperature for converting the hydrocarbons in this zone. 'Ehe steam also serves, by its partial pressure eiect, to materially reduce the effective pressure at which the hydrocarbon conversion reaction is conducted. By thus emare supplied to and burned in the regenerating vessel in contact `with the uidized bed of subdivided solid material in this zone. Provision is made in the case here illustrated for introducing the required auxiliary fuel into the regenerating vessel through line 29 and valve 3D. The fuel employed may be either liquid, gaseous or powdered solid fuel, gaseous or liquid fuel being ordinarily preferred rather than a solid fuel of high ash content.

When substantial quantities of steam are utilized in the reaction zone a large portion of the total heat required for conduct-ing the process will be utilized in its generation and in bringing it to desired reaction temperature. Since this heat is carried to a large extent by the solid particles, the r-ate at which the latter are circulated through the reaction and regenerating vessels can be controlled to obtain any desired degree of superheat for any reasonable quantity of steam, providing sufficient fuel is burned in the regenerating vessel. A special feature of the invention,

which should not be construed as limiting its broader aspects, provides for maintaining a local cyclic flow of subdivided solid material between and through the steam superheatng zone and of the regenerating zone without passing of the same through the reaction zone. By means of this provision the residence time and rate of circulation of the subdivided solid contact material through the reaction zone, wherein it contacts the hydrocarbons, may be controlled independently of the rate of circulation required to superheat the steam. This independent control is a highly desirable and advantageous feature of the invention.

Local circulation of contact material from the steam superheating zone to the regenerating zone is accomplished by directing a column thereof from the fluid bed in the steam superheating zone through standpipe 3i and through a suitable restriction, such as the yadjusted orifice or valve indicated at 32, into transfer line I@ wherein this that supplied to the transfer line through standpipe Hi, is commingled with the oxidizing gas introduced through line Il and valve i8 and is transported thereby to the duid bed in the regenerating vessel. Obviously, when desired, a separate transfer line may be employed for the solid material supplied from the reaction zone to the regenerating zone and for the solid material supplied from the steam superheating zone to the regenerating zone.

To prevent excessive compaction of the solid particles in the columns thereof passing through lines lll. 2li and 3l', relatively small quantities of suitable inert gas, such as steam, for example, may be introduced into these columns at one or a plurality of suitable points on the up-stream side of the respective valves l5, and 32, to flow upwardly through the columns countercurrent to the descending solid particles. Such gas may be introduced to standpipes il! and 3| through line 33 and the respective branch lines td and 35 controlled respectively by valves 36 and 31, and may be introduced to standpipe 24 through line 38 and valve 39.

In conducting operations of the invention is particularly directed, namely, the high temperature cracking of hydrocarbons to produce more valuable normally gaseous fractions, including butadiene, acetylene, etc., the operating conditions will depend, of course, upon the particular nature of employed, the product or products desired and the nature of the subdivided solid contact material, and these conditions may be selected to suit requirements. It is not the purpose of this disthe type to which closure to define optimum operating conditions for each of the wide variety of charging stocks, catalysts or inert contact masses which may be employed, nor for specific reactions which may be conducted within the scope of the invention, since the invention is believed to reside in the novel and advantageous features above outlined, rather than in the use of specific operating temperatures, pressures and the like.

In general, suitable operating conditions will correspond quite closely to those which have been previously utilized in conducting reactions of the same general type in a fixed bed process, in so far as fixed bed and fluid bed operations are comparable. However, the use of a fluidlike bed of contact material, as well as the use of steam, as herein provided, permits lower effective operating pressures in the reaction zone than have heretofore been obtainable with good economy in fixed bed operations. This favors the production of highly olenic gases from either normally liquid or normally gaseous charging stocks and results in higher yields of the desired products under otherwise suitable operating conditions, or at least reduces the yields of undesired products normally formed at higher pressures by undesirable secondary and side reactions.

To indicate the possible range of operating conditions we will consider, for example, the high temperature treatment of hydrocarbon distillates, such as kerosene or kerosene'distillate, naphtha, light gas oil and the like to produce appreciable yields of butadiene, employing relatively inert contact material, such as fine particles of dre-clay, quartz, silica or the like, which acts as a receptor for the combustible deposits and as a means of transferring heat from the exothermic regenerating step to the endothermic reaction. The temperature employed in the reaction zone may range, for example, from 1100 to 2000 F., or more. In fact its upper limit is fixed for practicable purposes, more by the available materials of construction than by other con-- sideration.

A weight ratio of solid contact material to oil entering the reaction zone per hour, ranging from 20:1 to 50:1, or thereabouts is preferably employed, although it may within the scope of the invention be as low as 5:1 or as high as 100:1.

I preferably employ sufficient steam to give an effective pressure of not more than a few pounds above atmospheric in the reactor, and substantial sub-atmospheric effective pressures give best rest results. The actual gauge pressure in the reactor may range from 50 pounds, or thereabouts, to as low as can be conveniently obtained. The molal ratio of steam to oil in the reaction zone may range from ltl to 10:1 or thereabouts, depending upon the gauge pressure at which it is desired to operate the reactor, a low gauge pressure obviously permitting' the use of less steam for the same effective operating pressure.

The average residence time for the solid contact material in the reaction zone is correlated with the ratio of solid contact material to oil entering the reaction zone and is maintained at a sufficiently low value to prevent the excessive accumulation of heavy deposits on the catalyst, which would retard heat transmission to the fluid reactants and cause agglomeration of the solid particles. On the other hand, it must be high enough that the heated solid material will transmit the necessary heat to the hydrocarbon reactants. A suitable average residence time will normally be within the range of to 30 minutes, depending primarily upon the cokeforming characteristics of the charging stock and the density of the contact material.

By virtue of the provisions of the invention the ratio of solid contact material to oil in the reaction zone is controllably independent of the ratio of contact material to steam. The latter may be the same as the ratio of contact material to oil or as much higher or' lower as is required.

I claim as my invention:

1. Apparatus for contacting finely divided solid particles with at least three iluid streams, comprising in combination, a combustion chamber, a iiuid superheating chamber and a reaction chamber, each being elongated vertically positioned chambers with the latter positioned above and in alignment with said superheating chamber, an inverted truncated cone-shaped partition between said superheating chamber and said reaction chamber forming a restricted opening therebetween, conduits from each of last said chambers which merge together in a single conin a manner suitable to transport particles to said combustion chamber, a conduit between said combustion chamber and said superheating chamber, a fluid inlet connecting with last said conduit in a manner suitable to transport particles to said superheating chamber, an inlet conduit terminating within said restricted opening of said partition, the outer surface of said each of said conduits, solid particle retaining means and iiuid outlets at the upper end of both the combustion and reaction chambers.

2. A unitary apparatus for the conversion of fluid reactants in the presence of inely divided solid particles and a superheated gaseous medium, which comprises in combination, a substantially vertical chamber having therein reaction and fluid superheating sections, said reaction section superimposed over and in vertical alignment with said iuid superheating section, with an inverted truncated cone-shaped partition between said sections forming a restricted opening therebetween, an inlet at the lower end of said uid superheating section for the introduction of nely divided particles and a fluid medium, and inlet conduit terminating within reaction chamber, particle separating and retaining means in the upper portion of said reaction section, a vapor outlet from said reaction section, and the particle withdrawal conduits from each of said sections with adjustable ow control means therein.

JERRY MCAFEE.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PA'I'ENTs Name Rial

Jahnig Sept. 10, 1946 Jahnig May 13, 1947 Murphree et al. Aug. 19, 1947 Number Date Allg. 22, 1944 2,407,371 

1. APPARATUS FOR CONTACTING FINELY DIVIDED SOLID PARTICLES WITH AT LEAST THREE FLUID STREAMS, COMPRISING IN COMBINATION, A COMBUSTION CHAMBER, A FLUID SUPERHEATING CHAMBER AND A REACTION CHAMBER, EACH BEING ELONGATED VERTICALLY POSITIONED CHAMBERS WITH THE LATTER POSITIONED ABOVE AND IN ALIGNMENT WITH SAID SUPERHEATING CHAMBER, AN INVERTED TRUNCATED CONE-SHAPED PARTITION BETWEEN SAID SUPERHEATING CHAMBER AND SAID REACTION CHAMBER FORMING A RESTRICTED OPENING THEREBETWEEN, CONDUITS FROM EACH OF LAST SAID CHAMBERS WHICH MERGE TOGETHER IN A SINGLE CONDUIT CONNECTING WITH SAID COMBUSTION CHAMBER, A GAS INLET CONNECTING WITH SAID MERGED CONDUITS IN A MANNER SUITABLE TO TRANSPORT PARTICLES TO SAID COMBUSTION CHAMBER, A CONDUIT BETWEEN SAID COMBUSTION CHAMBER AND SAID SUPERHEATING CHAMBER, A FLUID INLET CONNECTING WITH LAST SAID CONDUIT IN A MANNER SUITABLE TO TRANSPORT PARTICLES TO SAID SUPERHEATING CHAMBER, AN INLET CONDUIT TERMINATING WITHIN SAID RESTRICTED OPENING OF SAID PARTITION, THE OUTER SURFACE OF SAID INLET CONDUIT BEING IN CLOSE PROXIMITY TO THE PERIPHERY OF SAID RESTRICTED OPENING AND SAID INLET CONDUIT BEING DIRECTED UPWARDLY TOWARD SAID REACTION CHAMBER, WHEREBY FLUID REACTANT STREAM ISSUING FROM SAID INLET CONDUIT SERVES TO ASPIRATE PARTICLES AND SUPERHEATED FLUID MEDIUM FROM THE SUPERHEATING CHAMBER INTO THE REACTION CHAMBER, ADJUSTABLE FLOW CONTROL MEANS IN EACH OF SAID CONDUITS, SOLID PARTICLE RETAINING MEANS AND FLUID OUTLETS AT THE UPPER END OF BOTH THE COMBUSTION AND REACTION CHAMBERS. 